EP0351193A2 - Compositions de revêtement de surface - Google Patents

Compositions de revêtement de surface Download PDF

Info

Publication number
EP0351193A2
EP0351193A2 EP89307038A EP89307038A EP0351193A2 EP 0351193 A2 EP0351193 A2 EP 0351193A2 EP 89307038 A EP89307038 A EP 89307038A EP 89307038 A EP89307038 A EP 89307038A EP 0351193 A2 EP0351193 A2 EP 0351193A2
Authority
EP
European Patent Office
Prior art keywords
composition
dextrin
tackifier
weight
surfactant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP89307038A
Other languages
German (de)
English (en)
Other versions
EP0351193B1 (fr
EP0351193A3 (fr
Inventor
Mahinder Singh Mahil
John Mcnab Cruden
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harlow Chemical Co Ltd
Original Assignee
Harlow Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Harlow Chemical Co Ltd filed Critical Harlow Chemical Co Ltd
Publication of EP0351193A2 publication Critical patent/EP0351193A2/fr
Publication of EP0351193A3 publication Critical patent/EP0351193A3/fr
Application granted granted Critical
Publication of EP0351193B1 publication Critical patent/EP0351193B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
    • C09J103/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C

Definitions

  • This invention relates to surface coating compositions and to products employing them. More especially, it relates to compositions suitable for use as pressure sensitive adhesives.
  • Adhesive compositions of this type are often supplied to the user in organic solution, and are frequently based on acrylic ester polymers with or without a tackifying resin. There remains a need for a composition not requiring an organic solvent, which is capable of accepting high tackifier level without an unacceptable loss in adhesive strength, and which has higher shear strength than known compositions derived from acrylic ester polymers.
  • the present invention provides a composition
  • a composition comprising dextrin, a surfactant, a polymer a major proportion of the repeating units of which are derivable from an acrylate of at least one saturated aliphatic alcohol having from two to twelve carbon atoms, the composition optionally also containing a tackifier.
  • the dextrin level may be up to 7%, based on the total weight of dextrin, surfactant, and acrylate polymer (hereinafter referred to as "the specified components"); in the absence of tackifier, the maximum dextrin level is 3.5%, based on the total weight of the specified components.
  • the invention also provides the composition in the form of an aqueous dispersion, as well as in the form of a layer on a substrate.
  • composition is advantageously made by polymerizing an acrylic ester of at least one saturated aliphatic alcohol having from two to twelve carbon atoms in the presence of a surfactant and dextrin, the polymerization advantageously being carried out in an aqueous medium.
  • composition of the invention is made by the above-described procedure, some of the dextrin and some of the acrylate polymer will be bound together, in the form of a graft copolymer.
  • proportions of components said to be essential, advantageous, or preferred, however, this possibility is disregarded.
  • the dextrin level is advantageously at least 0.2%, and is preferably within the range of from 0.5% to 3.0%, by weight, of the specified components if no tackifier is present or within the range of from 0.5% to 5% if a tackifier is present. Below the 0.2% level, the increase in shear strength compared with an otherwise similar acrylate composition is not significant, while above the maxima the composition shows reduced tack.
  • the surfactant is present in the composition in a proportion of from 1 to 15, preferably from 5 to 10, percent by weight of the specified components.
  • the surfactant may be nonionic, anionic, cationic or amphoteric; and any one composition may contain two or more members of any one category or one or more members of two or more categories of surfactant.
  • condensation products of one or more molecules of ethylene oxide and a hydrophobe for example a condensate of octyl or nonyl phenol in which the alkyl chains may be linear or branched, with up to 100, advantageously between 4 and 40, moles of ethylene oxide; a condensate of ethylene oxide with a monohydric aliphatic alcohol, the chain of which may be linear or branched and which, advantageously, contains from 8 to 18 carbon atoms, and a condensate of ethylene oxide with a fatty acid or fatty acid amide.
  • ethylene oxide condensates of value include those with polypropylene oxide and acetylenic glycols.
  • anionic surfactants there may be mentioned the salts, preferably the alkali metal and ammonium salts, of alkyl sulphates and sulphonates or of alkyl aryl sulphonates, e.g., sodium lauryl sulphate, sodium dodecyl benzenesulphonate or disodium dodecyl diphenyl ether sulponate; salts of mono-and di-esters of sulphosuccinic acid, e.g., sodium di 2-ethylhexyl sulphosuccinate or disodium isododecyl sulphosuccinate; salts of alkyl sulphosuccinamates, of sulphated oils, of alkyl phosphates, or of ethoxylated alkyl phosphates.
  • salts of sulphated nonionic surfactants e.g., sodium lauryl ether sulphate
  • cationic surfactants there may be mentioned certain amino compounds, for example quaternary ammonium salts with long chain alkyl groups, for example, cetyl trimethylammonium bromide.
  • amphoteric surfactants may be mentioned the salts of alkyl sulpho betaines.
  • the polymer is advantageously present in the composition in a major proportion; preferably in a proportion within the range of from 65 to 95, and most preferably from 75 to 90, percent based on the weight of the specified components.
  • the specified components including tackifiers, advantageously represent at least 85% by weight of the solids content of the composition, preferably at least 95%.
  • Units derivable from, advantageously derived from, the acrylic ester of a monohydric saturated aliphatic alcohol with from two to twelve, advantageously from four to twelve, and preferably from four to eight, carbon atoms advantageously constitute at least 60%, preferably at least 70%, by weight of the polymer, and the polymer may consist of such units.
  • the polymer is a copolymer of the acrylic ester with ethylene and/or a vinyl ester, e.g., vinyl acetate or propionate, a proportion of acrylic ester lower than 70% is preferred.
  • the acrylic ester is n-butyl acrylate, 2-ethylhexyl acrylate, or a mixture thereof, though ethyl, iso-butyl, n-hexyl, n-heptyl, 2-ethylbutyl, and lauryl acrylates are also suitable. If a mixture of two or more acrylates is used, one of the acrylates is advantageously of an alcohol with at least 4 carbon atoms (and if butyl is advantageously n-butyl alcohol).
  • units other than the specified units of the polymer there may be mentioned units derived from acrylates of alcohols other than those specified, of methanol, aliphatic alcohols with 13 or more carbon atoms, alkaryl and aralkyl alcohols, alcohols with substituents, e.g., the haloalkanols and cyanoalkanols, acrylic esters of poly(ethylene and/or propylene oxide) and the monoalkyl or monoaryl ethers of such polyalkylene oxides; advantageously, the poly(alkylene oxide) has a chain length of from 2 to 30 units.
  • Vinyl esters are advantageous comonomers, preferably esters of saturated monocarboxylic acids with from 2 to 18 especially 2 to 12, carbon atoms.
  • vinyl acetate, propionate, 2-ethylhexanoate and laurate examples
  • Vinyl ethers for example vinyl iso-butyl ether, may usefully be incorporated in the composition, enhancing tack.
  • the mono and di esters of itaconic, maleic and fumaric acids with alcohols with from 1 to 8 carbon atoms, especially dibutyl fumarate, may also be incorporated.
  • Suitable monomers include styrene, substituted styrene, butadiene, isoprene, acrylonitrile, methacrylonitrile, ethylene, isobutylene, vinyl chloride, and vinylidene chloride.
  • Monomers other than those given above may be incorporated at relatively low levels, for example from 0.1% to 5.0%. These may be included to improve adhesion to certain substrates, to provide cross-linking of the polymer system, or to help to stabilize the polymer dispersion. Certain monomers can perform more than one of these functions simultaneously.
  • Monomers which may be used to improve adhesion to particular substrates include: unsaturated carboxylic acids, for example, acrylic acid, methacrylic acid, itaconic acid and fumaric acid; acrylamide and methacrylamide and their N-substituted derivatives, e.g., N-methylolacrylamide, N-t-butyl acrylamide, N-methoxymethyl methacrylamide, N-isobutoxy acrylamide; condensates of acrylamide or methacrylamide with glyoxylic acid; hydroxyalkyl esters of unsaturated carboxylic acids, for example, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, bis-hydroxypropyl itaconate; glycidyl methacrylate; monomers containing acetoacetate groups, e.g., allyl acetoacetate or the acetoacetate of 2-hydroxyethy
  • monomers with more than one polymerizable double bond which may be incorporated to introduce cross-linking and thus raise the overall molecular weight of the adhesive there may be mentioned: divinyl benzene, ethylene glycol dimethacrylate; trimethylol propane triacrylate; diallyl maleate, and hexane-1,6-diol dimethacrylate.
  • Monomers which may be incorporated to assist in the stabilization of the polymer latex include the unsaturated acids and amides listed above, and also monomers with sulphate, sulphonate or phosphate groups, for example sodium vinyl sulphonate; sodium styrene sulphonate; sodium acrylamido propane sulphonate; sodium 2-ethyl sulphato methacrylate; and sodium vinyl phosphate.
  • the polymer has a Tg, as measured by differential scanning calorimetry (DSC), of at most -20 o C.
  • DSC Tg of the polymer is in the range -50 o C to -70 o C, preferably from -65 o C to -70 o C.
  • the composition may also comprise additives to modify the rheology of the composition when in the form of a dispersion, or to improve mechanical or compounding stability.
  • additives are water soluble polymeric stabilizers, for example, polyvinyl alcohol, hydroxyethyl cellulose, sodium carboxymethyl cellulose, polyvinyl pyrrolidone and gum arabic.
  • the specified alkyl acrylate polymer, together with the tackifier, if present, will, however, advantageously represent a major proportion by weight of the macromolecular material in the composition, and preferably represents at least 75% by weight thereof.
  • compositions are prepared, as is preferred, by emulsion polymerization, any technique generally suitable for such polymerization may be employed.
  • the process is conveniently carried out at any temperature from 0 o C to 100 o C, but preferably from 20 o C to 90 o C.
  • a polymerization initiator is required; this is most conveniently chosen from products well known in emulsion polymerization, for example, ammonium peroxydisulphate, potassium peroxydisulphate, potassium peroxydiphosphate or hydrogen peroxide. At the lower temperatures these will normally be used in conjunction with a reducing agent such, for example, as sodium bisulphite, sodium formaldehyde sulphoxylate or ascorbic acid. These reducing agents may also be used conveniently with organic hydroperoxides such, for example, as t.butyl hydroperoxide or cumene hydroperoxide.
  • Another class of initiators which may conveniently be used are azo compounds such, for example, as azo bis isobutyronile or azo bis isobutyric acid.
  • the cationic initiator 2,2′-azobis (N,N′-­dimethylene isobutyramidine) dihydrochloride is especially suitable if a cationic dispersion is being prepared.
  • composition whether the dispersion resulting from the polymerization carried out as described above or otherwise, may be employed directly as an adhesive coating composition.
  • the composition is applied as an aqueous dispersion, advantageously with a solids content of at least 35% by weight, preferably at least 45% by weight.
  • the dispersion may be employed without further additives, but other components may be employed to obtain specific properties, e.g., colorants, antioxidants, bactericides, fungicides or additional solvents, e.g., xylene or acetone, plasticizers, e.g., phthalic or adipic acid esters, and thickeners, e.g., polyvinyl alcohol, water- or alkali-soluble polyacrylates, or polyethylene oxide diisocyanate condensates.
  • specific properties e.g., colorants, antioxidants, bactericides, fungicides or additional solvents, e.g., xylene or acetone
  • plasticizers e.g., phthalic or adipic acid esters
  • thickeners e.g., polyvinyl alcohol, water- or alkali-soluble polyacrylates, or polyethylene oxide diisocyanate condensates.
  • tackifiers especially tackifying resins.
  • suitable resins there may be mentioned those derived from rosin acids, obtained from, for example, gum or wood rosin, which may be stabilized by disproportionation, hydrogenation, dimerization or polymerization.
  • stabilized rosin acid esters the esters being of mono, or di or higher polyhydric alcohols, for example, one or more of methanol, ethanol, ethylene glycol, glycerol and pentaerythritol may be used.
  • Other tackifiers include low molecular weight polymers of styrene, alpha methyl styrene and cyclopentadiene.
  • the proportion of the total composition constituted by the tackifier if present, based on the total solids content of the composition may be up to 50% by weight.
  • One range of preferred compositions contains from 40% to 50% by weight of tackifier, such compositions being useful as general purpose adhesives; a second preferred range contains from 10 to 15% by weight of tackifier, such compositions having good low temperature properties.
  • the appropriate proportion of tackifier in the composition to some extent depends on the proportion of the dextrin in the said components, a higher proportion of tackifier enabling a higher dextrin content to be employed, giving the higher shear strength we have found to be associated with the use of dextrin while compensating at least in part for the loss in tack.
  • the dextrin is one obtainable by the hydrolysis of potato starch, since the composition in the form of an aqueous dispersion remains workable within a wide temperature range when such a dextrin is used. Materials employing dextrins obtainable from other starches are, however, also within the scope of the invention.
  • the dextrin has a viscosity, at 25 o C in a 37% by weight aqueous solution, of at most 100 MPas. measured in a Ostwald viscometer.
  • Suitable commercially available potato starch dextrins include those sold under the trade marks EMDEX and AVEDEX, especially Emdex 30 AN 45 and Avedex 36 LAC 14G and 37 LAC 19.
  • the initial charge was added to a polymerization reactor immersed in a thermostatically controlled water bath and fitted with a stirrer, reflux condenser, and the means for the continuous addition of monomers and the surfactant/initiator solution.
  • the reactor and its contents were heated to 60 o C at which temperatures 10% of the monomer charge was added followed by the initiator solutions.
  • the charge was then heated to 90 o C and held for thirty minutes to complete polymerization of the initial monomers.
  • Example 2 - 0.25
  • Example 3 - 0.50 " 4 - 0.75 " 5 - 1.00 " 6 - 1.50 " 7 - 2.00
  • Example 1 2 3 4 5 6 7 Solids Content,% 60.6 60.0 59.8 60.6 60.6 60.3 60.2 Particle Size (nm) 480 360 330 360 375 360 345 Brookfield Viscosity (cp) RVT 4/20 150 250 640 1220 1200 1580 2100 Dextrin as % of specified components (approx.) 0.0 0.1 0.83 1.25 1.65 2.49 3.32
  • the polymer emulsion was bar-coated directly on 36 micron Mylar D polyester film so as to achieve a continuous film, free from defects, with a dry coat weight of 20 g/m2.
  • the emulsion was dried at 90 o C in an oven with fan assisted air circulation.
  • the adhesive film was then laminated to a silicone coated release backing and stored at 23 o C ⁇ 2 o C and 50% ⁇ 5% R.H. for 24 hours before evaluation.
  • Example 9 The same basic formulation as Example 1 was used in the preparation of Example 8, with the monomer charge altered to a composition of 45% 2-ethylhexyl acrylate, 45% n-butyl acrylate and 10% vinyl acetate. Examples 9 to 12 were modified by the addition of Avedex 37 LAC 19 as before.
  • the latices formed had the following physical properties: Example 8 9 10 11 12 Dextrin, % on dispersion 0 0.25 0.50 0.75 1.00 Dextrin, % solids (approximate) 0 0.42 0.85 1.27 1.68 Solids Content 59.8 58.9 58.9 59.0 59.5 Particle Size (nm) 200 190 180 175 215 Brookfield Viscosity (Poise) 109 69 107 114 53
  • the Tg of the polymer of Example 12 was -54 o C; other polymers have similar values, with lower dextrin levels giving lower Tg's.
  • Example 13 was identical to Example 1 save for the use of acrylonitrile in place of methyl methacrylate.
  • Examples 14 to 22 were modified as before with the dextrin grade Avedex 37 LAC 19.
  • the latices obtained had the following physical properties: Example Dextrin Level,% Solids Content Particle Size (nm) Brookfield Viscosity RVT 4/20 cp (a) (b) 13. 0 60.6 450 90 14. 0.25 0.41 60.5 360 240 15. 0.50 0.83 60.6 420 620 16. 0.75 1.24 60.7 490 810 17. 1.00 1.66 60.4 360 970 18. 1.50 2.48 60.4 530 2700 19. 2.00 3.33 60.0 470 2500 (a) on dispersion (b) on solids (approximate)
  • cationic latices were prepared in a manner similar to Example 1.
  • the initial charge was added to the reactor and heated to 60 o C at which temperature 10% of the monomer mixture was added followed by the initiator solution.
  • the reactor was heated to 90 o C and held for thirty minutes to allow the initial polymerization to take place.
  • the simultaneous addition was started of the monomers and the stabilizer/initiator solution. This was completed in five fours.
  • the final initiator solution was then added and the emulsion held at 90 o C for a further hour before cooling.
  • the emulsions produced had the following properties: Example Solids Content,% Particle Size (nm) Brookfield Viscosity RVT 4/20 cp 20. 49.7 275 400 21. 52.5 300 490

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Paints Or Removers (AREA)
  • Pens And Brushes (AREA)
  • Materials For Medical Uses (AREA)
EP89307038A 1988-07-12 1989-07-11 Compositions de revêtement de surface Expired - Lifetime EP0351193B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8816515 1988-07-12
GB888816515A GB8816515D0 (en) 1988-07-12 1988-07-12 Surface coating compositions

Publications (3)

Publication Number Publication Date
EP0351193A2 true EP0351193A2 (fr) 1990-01-17
EP0351193A3 EP0351193A3 (fr) 1991-09-25
EP0351193B1 EP0351193B1 (fr) 1996-01-03

Family

ID=10640276

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89307038A Expired - Lifetime EP0351193B1 (fr) 1988-07-12 1989-07-11 Compositions de revêtement de surface

Country Status (5)

Country Link
EP (1) EP0351193B1 (fr)
AT (1) ATE132520T1 (fr)
DE (1) DE68925311T2 (fr)
ES (1) ES2083971T3 (fr)
GB (2) GB8816515D0 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0466911A1 (fr) * 1990-02-07 1992-01-22 Avery Dennison Corp Substance adhesive a emulsion acrylique pouvant etre rendue collante, presentant des performances excellentes a basse temperature.
EP0699692A3 (fr) * 1994-09-02 1997-10-22 Hoechst Ag Dispersions aqueuses pour adhésifs
US6121508A (en) * 1995-12-29 2000-09-19 3M Innovative Properties Company Polar, lipophilic pressure-sensitive adhesive compositions and medical devices using same
EP0728166B2 (fr) † 1993-11-10 2008-09-17 Minnesota Mining And Manufacturing Company Adhesifs autocollants
WO2016008814A1 (fr) * 2014-07-15 2016-01-21 Basf Se Adhésifs sensibles à la pression

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6245838B1 (en) 1998-02-03 2001-06-12 3M Innovative Properties Company Method of suspension polymerization of (meth)acrylic monomers using dextrin, and polymer beads resulting from that method

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58191777A (ja) * 1982-05-06 1983-11-09 Daio Kakoshi Kogyo Kk 合成樹脂板用の帯電防止を兼ねた再剥離可能な表面保護材
EP0297900A2 (fr) * 1987-07-03 1989-01-04 Harlow Chemical Company Limited Compositions adhésives et feuilles auto-adhésives

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1278813A (en) * 1969-08-27 1972-06-21 High Polymer Chemical Ind Ltd Method of preparation of acrylic polymer latices
DE2659133C2 (de) * 1976-12-28 1978-09-21 Roehm Gmbh, 6100 Darmstadt Verfahren zur Herstellung von blockfesten Überzügen

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58191777A (ja) * 1982-05-06 1983-11-09 Daio Kakoshi Kogyo Kk 合成樹脂板用の帯電防止を兼ねた再剥離可能な表面保護材
EP0297900A2 (fr) * 1987-07-03 1989-01-04 Harlow Chemical Company Limited Compositions adhésives et feuilles auto-adhésives

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPIL, accession no. 83-846882 [51], Derwent Publications Ltd, London, GB; & JP-A-58 191 777 (DAIO KAKOSHI KOGYO) 09-11-1983 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0466911A1 (fr) * 1990-02-07 1992-01-22 Avery Dennison Corp Substance adhesive a emulsion acrylique pouvant etre rendue collante, presentant des performances excellentes a basse temperature.
EP0466911A4 (en) * 1990-02-07 1993-04-14 Avery Dennison Corporation Tackifiable acrylic emulsion pressure-sensitive adhesive having excellent low-temperature performance
EP0728166B2 (fr) † 1993-11-10 2008-09-17 Minnesota Mining And Manufacturing Company Adhesifs autocollants
EP0699692A3 (fr) * 1994-09-02 1997-10-22 Hoechst Ag Dispersions aqueuses pour adhésifs
US6121508A (en) * 1995-12-29 2000-09-19 3M Innovative Properties Company Polar, lipophilic pressure-sensitive adhesive compositions and medical devices using same
WO2016008814A1 (fr) * 2014-07-15 2016-01-21 Basf Se Adhésifs sensibles à la pression
CN106715626A (zh) * 2014-07-15 2017-05-24 巴斯夫欧洲公司 压敏粘合剂
AU2015289326B2 (en) * 2014-07-15 2018-08-30 Basf Se Pressure sensitive adhesives
CN106715626B (zh) * 2014-07-15 2020-11-20 巴斯夫欧洲公司 压敏粘合剂

Also Published As

Publication number Publication date
GB8915821D0 (en) 1989-08-31
GB2220668B (en) 1992-05-13
EP0351193B1 (fr) 1996-01-03
DE68925311T2 (de) 1996-09-19
DE68925311D1 (de) 1996-02-15
GB8816515D0 (en) 1988-08-17
EP0351193A3 (fr) 1991-09-25
ES2083971T3 (es) 1996-05-01
ATE132520T1 (de) 1996-01-15
GB2220668A (en) 1990-01-17

Similar Documents

Publication Publication Date Title
US4507429A (en) Pressure sensitive adhesives with improved shear resistance
CA1156776A (fr) Procede non tensio-actif pour la production de colles de latex tenant a la pression
EP0608371B1 (fr) Ameliorations relatives a des compositions adhesives autocollantes pouvant etre refondues
US4716194A (en) Removable pressure sensitive adhesive
JP2525614B2 (ja) 感圧接着剤
US5461103A (en) Process for producing a stable aqueous pressure sensitive adhesive polymer emulsion
JPS5818931B2 (ja) 粘着基剤用酢酸ビニル−エチレン共重合体エマルジョン
PL187497B1 (pl) Kompozycja kleju przylepcowego i jej zastosowanie
US20030077443A1 (en) Blends of high Tg polymer emulsions and pressure sensitive adhesive polymer emulsions useful as pressure sensitive adhesives
US4694056A (en) Pressure sensitive adhesives prepared by polymerization in the presence of ethoxylated acetylenic tertiary glycol
US3900610A (en) Process of making a pressure sensitive adhesive article
JP2895237B2 (ja) エマルションポリマーをベースにした感圧接着剤
US4725639A (en) Process for preparing pressure sensitive adhesives
EP0282710B1 (fr) Adhésifs sensibles à la pression utilisés sur des substrats vinyliques
US5185212A (en) Acetoacetoxy-alkyl acrylate-containing pressure sensitive adhesives manufactured articles
EP0277516B1 (fr) Compositions adhésives pour utilisation sur des substrats vinyliques
US5055504A (en) Surface coating compositions
EP0351193B1 (fr) Compositions de revêtement de surface
EP0332860B1 (fr) Copolymères d'éthylène, d'acétate de vinyle, de dioctylmaléate, et de 2-éthylhexyl acrylate
JP3670049B2 (ja) ディレードタック型粘着剤組成物
EP0297900B1 (fr) Compositions adhésives et feuilles auto-adhésives
US4892917A (en) Adhesive compositions for use on vinyl substrates
US4056497A (en) Acrylic ester copolymers capable of being cross-linked
JPS62141081A (ja) エチレン／ビニルアセテ−ト／ジオクチルマレエ−ト三元共重合体により成る感圧接着剤組成物
EP0586966A2 (fr) Adhésifs sensibles à la pression à base aqueuse et à cohésion élevée

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE DE ES FR GB IT NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE DE ES FR GB IT NL SE

17P Request for examination filed

Effective date: 19911022

17Q First examination report despatched

Effective date: 19930705

RBV Designated contracting states (corrected)

Designated state(s): AT BE DE ES FR IT NL SE

17Q First examination report despatched

Effective date: 19950209

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE DE ES FR IT NL SE

REF Corresponds to:

Ref document number: 132520

Country of ref document: AT

Date of ref document: 19960115

Kind code of ref document: T

REF Corresponds to:

Ref document number: 68925311

Country of ref document: DE

Date of ref document: 19960215

ITF It: translation for a ep patent filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19960403

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2083971

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20000710

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20000711

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20000712

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20000719

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20000728

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20000918

Year of fee payment: 12

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010711

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010712

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010731

BERE Be: lapsed

Owner name: HARLOW CHEMICAL CY LTD

Effective date: 20010731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020329

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20020201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020501

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20020810

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050711